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CA2458955A1 - A process for making rare earth metal oxide-coated microporous materials - Google Patents

A process for making rare earth metal oxide-coated microporous materials Download PDF

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CA2458955A1
CA2458955A1 CA002458955A CA2458955A CA2458955A1 CA 2458955 A1 CA2458955 A1 CA 2458955A1 CA 002458955 A CA002458955 A CA 002458955A CA 2458955 A CA2458955 A CA 2458955A CA 2458955 A1 CA2458955 A1 CA 2458955A1
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rare earth
earth metal
zeolite
colloidal dispersion
metal oxide
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CA2458955C (en
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James L. Woodhead
Stanislav M. Snaidr
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Neo International Corp
Rothmans Benson and Hedges Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D1/00—Cigars; Cigarettes
    • A24D1/02—Cigars; Cigarettes with special covers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

A process that provides a catalytic rare earth oxide-coated microporous free - flowing bulk particulate wherein the amount of metal oxide coated thereon is high, without jeopardizing the effectiveness of the material. The rare earth metal oxide coated on the outer surface may be in the range of 20 to 70% by weight based on the total equivalent rare earth metal oxide and microporous particulate material content. In particular, a zeolite free-flowing bulk particulate having high loadings of rare earth metal oxide tends to be quite stable. For instance, when the rare earth metal oxide-coated zeolite free- flowing bulk particulate has been heat treated at tempertures less than abou t 200~C and then slurried in water, typically, less than 30% by weight of the rare earth metal oxide (based of the total equivalent rare earth metal oxide content) is found to leach into water. This material has been found to have minimal leachability when heat treated above 400~C.

Claims (95)

1. A process for making a catalytic rare earth metal oxide-coated microporous particulate material having greater than 20% by weight of said rare earth metal oxide coated on outer surfaces of said microporous particulate material, based on the total equivalent rare earth metal oxide and microporous particulate material content, said process comprising the steps of:
i) combining an amount of a colloidal dispersion of rare earth metal oxide hydrate with a compatible microporous particulate material to form a slurry, the amount of the colloidal dispersion being sufficient to provide, when heat treated as per step (ii), greater than 20% by weight of the rare earth metal oxide, said microporous particulate material having an average pore size of less than 20.ANG. and said colloidal dispersion having a particle size of at least 20.ANG., to position thereby, said colloidal dispersion on said outer surfaces of said microporous particulate material; and ii) heat treating said slurry at a temperature below about 200°C, above about 400°C, or sequential combinations thereof wherein said slurry is heat treated, firstly, at temperatures below about 200°C and secondly, above about 400°C, to fix the resultant rare earth metal oxide on said outer surfaces of said microporous particulate material, to provide a free flowing bulk particulate.
2. The process of claim 1, wherein said microporous particulate material is a compatible aluminosilicate.
3. The process of claim 2, wherein said microporous particulate material is a compatible zeolite particulate material.
4. The process of claim 3, wherein said slurry is heat treated, firstly, at temperatures below about 200°C and secondly, above about 400°C.
5. The process of claim 4, wherein the rare earth metal oxide is selected from the group consisting of oxides of lanthanide metals, yttrium, scandium and a mixture thereof.
6. The process of claim 5, wherein the rare earth metal oxide is an oxide of cerium.
7. The process of claim 3, wherein said colloidal dispersion has a pH of less than 4.2 and said colloidal dispersion is crystalline.
8. The process of claim 1, wherein said process comprises a further step (iii) that includes milling said rare earth metal oxide coated microporous particulate material to provide particle sizes in the range of 1 to 25 microns.
9. The process of claim 1, wherein said slurry is heat treated using spray drying, tray drying, freeze drying, solvent drying, flash drying techniques or a mixture thereof.
10. The process of claim 3, wherein said colloidal dispersion is made from a rare earth metal salt substrate selected from the group consisting of a rare earth metal nitrate, a rare earth metal chloride, a rare earth metal acetate, a rare earth metal perchlorate and a mixture thereof.
11. The process of claim 3, wherein said colloidal dispersion is made from a lanthanide metal salt substrate selected from the group consisting of a lanthanide metal nitrate, a lanthanide metal chloride, a lanthanide metal acetate, a lanthanide metal perchlorate and a mixture thereof.
12. The process of claim 3, wherein said colloidal dispersion is dried to a gel and subsequently reconstituted in water to form said colloidal dispersion used in step (i).
13. The process of claim 3, wherein said zeolite is mixed with water and an acid is added to provide a pH of less than 4.2.
14. The process of claim 3, wherein said zeolite is mixed with water and provides a pH of less than 4.2.
15. The process of claim 3, wherein said colloidal dispersion is prepared to a predetermined controlled range of colloidal particle sizes of 20 to 50.ANG., 50 to 70.ANG. or 100 to 150.ANG..
16. The process of claim 15, wherein preparation of said colloidal dispersion, having said predetermined particle size of 20 to 50.ANG., comprises the steps of:
a) mixing a base and hydrogen peroxide with a hydrolyzable rare earth metal salt solution, yielding a rare earth metal hydroxide solution; and b) adding a strong acid to the rare earth metal hydroxide solution to provide the colloidal dispersion of rare earth metal oxide hydrate, wherein the strong acid is capable of deaggregating the colloidal dispersion of rare earth metal oxide hydrate.
17. The process of claim 15, wherein preparation of said colloidal dispersion, having said predetermined particle size of 50 to 70.ANG., comprises the steps of:
a) mixing a base with a hydrolyzable rare earth metal salt solution, whereby air is bubbled into said solution, yielding a rare earth metal hydroxide solution; and b) adding a strong acid to the rare earth metal hydroxide solution to provide the colloidal dispersion of rare earth metal oxide hydrate, wherein the strong acid is capable of deaggregating the colloidal dispersion of rare earth metal oxide hydrate.
18. The process of claim 15, wherein preparation of said colloidal dispersion, having said predetermined particle size of 100 to 150.ANG., comprises the steps of:
a) mixing a base with a hydrolyzable rare earth metal salt solution, in which the rare earth metal has two oxidation states;
b) allowing the hydrolyzable rare earth metal salt solution to slowly oxidize in air to yield a rare earth metal hydroxide solution; and c) adding a strong acid to the rare earth metal hydroxide solution to provide the colloidal dispersion of rare earth metal oxide hydrate, wherein the strong acid is capable of deaggregating the colloidal dispersion of rare earth metal oxide hydrate.
19. The process of claim 16, wherein the strong acid is selected from the group consisting of nitric acid, hydrochloric acid and perchloric acid.
20. The process of claim 17, wherein the strong acid is selected from the group consisting of nitric acid, hydrochloric acid and perchloric acid.
21. The process of claim 18, wherein the strong acid is selected from the group consisting of nitric acid, hydrochloric acid and perchloric acid.
22. The process of claim 19, wherein the strong acid is nitric acid and said colloidal dispersion of rare earth metal oxide hydrate comprises nitrate ions.
23. The process of claim 20, wherein the strong acid is nitric acid and said colloidal dispersion of rare earth metal oxide hydrate comprises nitrate ions.
24. The process of claim 21, wherein the strong acid is nitric acid and said colloidal dispersion of rare earth metal oxide hydrate comprises nitrate ions.
25. The process of claim 22, wherein said free flowing bulk particulate is nitrate ion-free.
26. The process of claim 23, wherein said free flowing bulk particulate is nitrate ion-free.
27. The process of claim 24, wherein said free flowing bulk particulate is nitrate ion-free.
28. The process according to claim 16, wherein the rare earth metal salt is selected from the group consisting of a rare earth metal nitrate, a rare earth metal chloride, a rare earth metal acetate, a rare earth metal perchlorate and a mixture thereof.
29. The process according to claim 17, wherein the rare earth metal salt is selected from the group consisting of a rare earth metal nitrate, a rare earth metal chloride, a rare earth metal acetate, a rare earth metal perchlorate and a mixture thereof.
30. The process according to claim 18, wherein the rare earth metal salt is selected from the group consisting of a rare earth metal nitrate, a rare earth metal chloride, a rare earth metal acetate, a rare earth metal perchlorate and a mixture thereof.
31. The process according to claim 16, wherein the rare earth metal is selected from the group consisting of lanthanide metals, yttrium, scandium and a mixture thereof.
32. The process according to claim 17, wherein the rare earth metal is selected from the group consisting of lanthanide metals, yttrium, scandium and a mixture thereof.
33 33. The process according to claim 18, wherein the rare earth metal is selected from the group consisting of cerium, europium and a mixture thereof.
34. The process of claim 1, wherein said microporous particulate material has a pore diameter less than 10.ANG..
35. The process of claim 3 wherein the colloidal dispersion has a pH of less than 4.2 and said cerium oxide hydrates are crystalline.
36. The process of claim 3, wherein said process comprises a further step (iii) that includes milling said rare earth metal oxide coated zeolite particulate material to provide particle sizes in the range of 1 to 25 microns.
37. The process of claim 3, wherein said slurry is heat treated using spray drying, tray drying, freeze drying, solvent drying, flash drying techniques and a mixture thereof.
38. The process of claim 3, wherein said colloidal dispersion of cerium oxide hydrates is made from a cerium salt substrate selected from the group consisting of a cerium nitrate, cerium chloride, cerium acetate, cerium perchlorate and a mixture thereof.
39. The process of claim 3, wherein said colloidal dispersion is dried to a gel and subsequently reconstituted in water to form said colloidal dispersion used in step (i).
40. The process of claim 3, wherein said zeolite is mixed with water and an acid is added to provide a pH of less than 4.2.
41. The process of claim 3, wherein said zeolite is mixed with water and provides a pH of less than 4.2.
42. The process of claim 3, wherein said colloidal dispersion is prepared to a predetermined controlled range of colloidal particle sizes of 20 to 50.ANG., 50 to 70.ANG. or 100 to 150.ANG..
43. The process of claim 42, wherein preparation of said colloidal dispersion, having said predetermined particle size of 20 to 50.ANG., comprises the steps of:
a) mixing a base and hydrogen peroxide with a hydrolyzable cerium salt solution, yielding a cerium (IV) hydroxide solution; and b) adding a strong acid to said cerium (IV) hydroxide solution to provide the colloidal dispersion of cerium oxide hydrate, wherein the strong acid is capable of deaggregating the colloidal dispersion of cerium oxide hydrate oxide hydrate.
44. The process of claim 42, wherein preparation of said colloidal dispersion, having said predetermined particle size of 50 to 70.ANG., comprises the steps of:
a) mixing a base with a hydrolyzable cerium salt solution, whereby air is bubbled into said solution, yielding a cerium (IV) hydroxide solution;
and b) adding a strong acid to said cerium (IV) hydroxide solution to provide the colloidal dispersion of cerium oxide hydrate, wherein the strong acid is capable of deaggregating the colloidal dispersion of cerium oxide hydrate oxide hydrate.
45. The process of claim 42, wherein preparation of said colloidal dispersion, having said predetermined particle size of 100 to 150.ANG., comprises the steps of:
a) mixing a base with a hydrolyzable cerium salt solution;
b) allowing the hydrolyzable cerium salt solution to slowly oxidize in air to yield a cerium (IV) hydroxide solution; and c) adding a strong acid to said cerium (IV) hydroxide solution to provide the colloidal dispersion of cerium oxide hydrate, wherein the strong acid is capable of deaggregating the colloidal dispersion of cerium oxide hydrate oxide hydrate.
46. The process of claim 43, wherein the strong acid is selected from the group consisting of nitric acid, hydrochloric acid and perchloric acid.
47. The process of claim 44, wherein the strong acid is selected from the group consisting of nitric acid, hydrochloric acid and perchloric acid.
48. The process of claim 45, wherein the strong acid is selected from the group consisting of nitric acid, hydrochloric acid and perchloric acid.
49. The process of claim 46, wherein the strong acid is nitric acid and said colloidal dispersion of cerium oxide hydrate comprises nitrate ions.
50. The process of claim 47, wherein the strong acid is nitric acid and said colloidal dispersion of cerium oxide hydrate comprises nitrate ions.
51. The process of claim 48, wherein the strong acid is nitric acid and said colloidal dispersion of cerium hydrate comprises nitrate ions.
52. The process of claim 49, wherein said free flowing bulk particulate is nitrate ion-free.
53. The process of claim 50, wherein said free flowing bulk particulate is nitrate ion-free.
54. The process of claim 51, wherein said free flowing bulk particulate is nitrate ion-free.
55. The process according to claim 43, wherein the cerium salt is selected from the group consisting of a cerium nitrate, a cerium chloride, a cerium acetate, a cerium perchlorate and a mixture thereof.
56. The process according to claim 44, wherein the cerium salt is selected from the group consisting of a cerium nitrate, a cerium chloride, a cerium acetate, a cerium perchlorate and a mixture thereof.
57. The process according to claim 45, wherein the cerium salt is selected from the group consisting of a cerium nitrate, a cerium chloride, a cerium acetate, a cerium perchlorate and a mixture thereof.
58. The process of claim 49, wherein the mole ratio of nitrate ions to cerium oxide in said colloidal dispersion is in the range of 0.12 to 0.25.
59. The process of claim 50, wherein the mole ratio of nitrate ions to cerium oxide in said colloidal dispersion is in the range of 0.12 to 0.25.
60. The process of claim 51, wherein the mole ratio of nitrate ions to cerium oxide in said colloidal dispersion is in the range of 0.12 to 0.25.
61. The process of claim 3, wherein said rare earth metal oxide coated on the outer surface is in the range of 20 to 70% by weight based on the total equivalent rare earth metal oxide and zeolite content.
62. The process of claim 61, wherein said rare earth metal oxide is cerium oxide.
63. The process of claim 3, wherein the zeolite is represented by the formula M m M'n M"P[aAlO2 .cndot. b SiO2 .cndot. cTO2]

wherein M is a monovalent cation, M' is a divalent ration, M" is a trivalent ration, a, b, c, n, m, and p are numbers which reflect the stoichiometric proportions, c, m, n or p can also be zero, Al and Si are tetrahedrally coordinated Al and Si atoms, and T is a tetrahedrally coordinated metal atom being able to replace Al or Si, the ratio of b/a of the zeolite or the zeolite-like material, has a value of about 5 to about 300 and the micropore size of the zeolite is within the range of 5 to .ANG..
64. The process of claim 3, wherein the zeolite is selected from the group consisting of silicalite zeolites, faujasites, X, Y and L zeolites, .beta.-zeolites, Mordenite zeolites and ZSM zeolites and a mixture thereof.
65. The process of claim 3, wherein the zeolite is selected from the group consisting of hydrophobic, mildly hydrophobic zeolites, and a mixture thereof, which have an affinity for hydrophobic and mildly hydrophobic organic compounds.
66. A catalytic rare earth metal oxide-coated zeolite free-flowing bulk particulate comprising:
a zeolite particulate material;
a rare earth metal oxide;
said zeolite particulate material having an average pore size of less than 20.ANG.; and greater than 20% by weight of said rare earth metal oxide coated on outer surfaces of said zeolite particulate material, based on the total, equivalent rare earth metal oxide and zeolite content.
67. The free-flowing bulk particulate of claim 66, wherein the rare earth metal oxide is selected from the group consisting of oxides of lanthanide metals, yttrium, scandium and a mixture thereof.
68. The free-flowing bulk particulate of claim 67, wherein the rare earth metal oxide is an oxide of cerium.
69. The free-flowing bulk particulate of claim 66, wherein said rare earth metal oxide coated on the outer surface is in the range of 20 to 70% by weight based on the total equivalent rare earth metal oxide and zeolite content.
70. The free-flowing bulk particulate of claim 67, wherein said lanthanide metal oxide coated on the outer surface is in the range of 20 to 70% by weight based on the total equivalent cerium oxide and zeolite content.
71. The free-flowing bulk particulate of claim 68, wherein said cerium oxide coated on the outer surface is in the range of 20 to 70% by weight based on the total equivalent cerium oxide and zeolite content.
72. The free-flowing bulk particulate of claim 66 further comprises particle sizes in the range of 1 to 25 microns.
73. The free-flowing bulk particulate of claim 66, wherein said free flowing bulk particulate is nitrate ion-free.
74. The free-flowing bulk particulate of claim 66, wherein said zeolite particulate material has a pore diameter less than 10.ANG..
75. The process of claim 66, wherein the zeolite is represented by the formula M m M' n M"p[aAlO2 .cndot. b SiO2 .cndot. c TO2]

wherein M is a monovalent cation, M' is a divalent cation, M" is a trivalent cation, a, b, c, n, m, and p are numbers which reflect the stoichiometric proportions, c, m, n or p can also be zero, Al and Si are tetrahedrally coordinated Al and Si atoms, and T is a tetrahedrally coordinated metal atom being able to replace Al or Si, the ratio of b/a of the zeolite or the zeolite-like material, has a value of about 5 to about 300 and the micropore size of the zeolite is within the range of 5 to .ANG..
76. The process of claim 67, wherein the zeolite is represented by the formula M m M' n M"p[aAlO2 .cndot. b. SiO2 .cndot. cTO2]
wherein M is a monovalent cation, M' is a divalent cation, M" is a trivalent cation, a, b, c, n, m, and p are numbers which reflect the stoichiometric proportions, c, m, n or p can also be zero, Al and Si are tetrahedrally coordinated Al and Si atoms, and T is a tetrahedrally coordinated metal atom being able to replace Al or Si, the ratio of b/a of the zeolite or the zeolite-like material, has a value >5 and the micropore size of the zeolite is within the range of 5 to 13 .ANG..
77. The process of claim 68, wherein the zeolite is represented by the formula Mm M'nM"p[aAlO2 ~ b SiO2 ~ cTO2]
wherein M is a monovalent cation, M' is a divalent cation, M" is a trivalent cation, a, b, c, n, m, and p are numbers which reflect the stoichiometric proportions, c, m, n or p can also be zero, Al and Si are tetrahedrally coordinated A1 and Si atoms, and T is a tetrahedrally coordinated metal atom being able to replace Al or Si, the ratio of b/a of the zeolite or the zeolite-like material, has a value >5 and the micropore size of the zeolite is within the range of 5 to 13 .ANG.
78. The free-flowing bulk particulate of claim 66, wherein the zeolite is selected from the group consisting of silicalite zeolites, faujasites, X, Y
and L
zeolites, .beta.-zeolites, Mordenite zeolites and ZSM zeolites and a mixture thereof.
79. The free-flowing bulk particulate of claim 67, wherein the zeolite is selected from the group consisting of silicalite zeolites, faujasites, X, Y
and L
zeolites, .beta.-zeolites, Mordenite zeolites and ZSM zeolites and a mixture thereof.
80. The free-flowing bulk particulate of claim 68, wherein the zeolite is selected from the group consisting of silicalite zeolites, faujasites, X, Y
and L
zeolites, .beta.-zeolites, Mordenite zeolites and ZSM zeolites and a mixture thereof.
81. The free-flowing bulk particulate of claim 66, wherein the zeolite is selected from the group consisting of hydrophobic, mildly hydrophobic zeolites, and a mixture thereof, which have an affinity for hydrophobic and mildly hydrophobic organic compounds.
82. The free-flowing bulk particulate of claim 66, wherein said zeolite particulate material has a pH of less than 4.2.
83. The free-flowing bulk particulate of claim 66, wherein less than 30% by weight of the rare earth metal oxide (based on the total equivalent rare earth metal oxide content) is found to leach into water when the rare earth metal oxide-coated zeolite free-flowing bulk particulate is slurried in water.
84. The free-flowing bulk particulate of claim 66, wherein less than 30% by weight of the cerium oxide (based on the total equivalent cerium oxide content) is found to leach into water when the cerium oxide-coated zeolite free-flowing bulk particulate is slurried in water.
85. A process for making a catalytic rare earth metal oxide-coated zeolite particulate material having at least 1% by weight of said rare earth metal oxide coated on outer surfaces of said zeolite particulate material, based on the total equivalent rare earth metal oxide and zeolite content, said process comprising the steps of:
i) combining an amount of a colloidal dispersion of rare earth metal oxide hydrate with a compatible zeolite particulate material to form a slurry, the amount of the colloidal dispersion being sufficient to provide, when heat treated as per step (ii), greater than 1.0% by weight of the rare earth metal oxide, said zeolite particulate material having an average pore size of less than 20.ANG. and said colloidal dispersion having a particle size of at least 20.ANG., to position thereby, said colloidal dispersion on said outer surfaces of said zeolite;
and ii) heat treating said slurry at a temperature below about 200°C, above about 400°C to about less than 550°C, or sequential combinations thereof wherein said slurry is heat treated, firstly, at temperatures below about 200°C
and secondly, above about 400°C but less than 550 °C, to fix the resultant rare earth metal oxide on said outer surfaces of said zeolite particulate material, to provide a free flowing bulk particulate.
86. A process for making a catalytic cerium oxide-coated zeolite particulate material having at least 1 % by weight of said cerium oxide coated on outer surfaces of said zeolite particulate material, based on the total equivalent cerium and zeolite content, said process comprising the steps of:
i) combining an amount of a colloidal dispersion of cerium oxide hydrate with a compatible zeolite particulate material to form a slurry, the amount of the colloidal dispersion being sufficient to provide, when heat treated as per step (ii), greater than 1.0% by weight of the cerium oxide, said zeolite particulate material having an average pore size of less than 20.ANG.
and said colloidal dispersion having a particle size of at least 20.ANG., to position thereby, said colloidal dispersion on said outer surfaces of said zeolite; and ii) heat treating said slurry at a temperature below about 200°C, above about 400°C to about less than 550°C, or sequential combinations thereof wherein said slurry is heat treated, firstly, at temperatures below about 200°C
and secondly, above about 400°C but less than 550°C, to fix the resultant cerium oxide on said outer surfaces of said zeolite particulate material, to provide a free flowing bulk particulate.
87. A process for making a catalytic rare earth metal oxide-coated zeolite particulate material having at least 1 % by weight of said rare earth metal oxide coated on outer surfaces of said zeolite particulate material, based on the total equivalent rare earth metal oxide and zeolite content, said process comprising the steps of:

i) combining an amount of a colloidal dispersion of rare earth metal hydrate with a compatible zeolite particulate material having a pH of less than about 4.2 to form a slurry, the amount of the colloidal dispersion being sufficient to provide, when heat treated as per step (ii), greater than 1.0%
by weight of the rare earth metal oxide, said zeolite particulate material having an average pore size of less than 20.ANG. and said colloidal dispersion having a particle size of at least 20.ANG., to position thereby, said colloidal dispersion on said outer surfaces of said zeolite; and ii) heat treating said slurry at a temperature below about 200°C, above about 400°C, or sequential combinations thereof wherein said slurry is heat treated, firstly, at temperatures below about 200°C and secondly, above about 400°C, to fix the resultant rare earth metal oxide on said outer surfaces of said zeolite particulate material, to provide a free flowing bulk particulate.
88. A process for making a catalytic rare earth metal oxide-coated zeolite particulate material having at least 1.0% by weight of said rare earth metal oxide coated on outer surfaces of said zeolite particulate material, based on the total equivalent rare earth metal oxide and zeolite content, said process comprising the steps of:
i) combining an amount of a colloidal dispersion of rare earth metal oxide hydrate with a compatible zeolite particulate material to form a slurry, the amount of the colloidal dispersion being sufficient to provide, when heat treated as per step (ii), at least 1.0% by weight of the rare earth metal oxide, said zeolite particulate material having an average pore size of less than about 20.ANG. and said colloidal dispersion having a particle size of at least about 20.ANG., to position thereby, said colloidal dispersion on said outer surfaces of said zeolite; and ii) heat treating said slurry at a temperature below about 200°C to fix the resultant rare earth metal oxide on said outer surfaces of said zeolite particulate material, to provide a free flowing bulk particulate.
89. A process for making a catalytic rare earth metal oxide-coated microporous particulate material having the rare earth metal oxide coated on outer surfaces of said microporous particulate material, said process comprising the steps of i) combining an amount of a colloidal dispersion of rare earth metal oxide hydrate with a compatible microporous particulate material to form a slurry, said microporous particulate material having an average pore size less than the particle size of said colloidal dispersion, to position thereby said colloidal dispersion on the outer surfaces of said microporous particulate material; and ii) heat treating said slurry to fix the rare earth metal oxide to the outer surfaces of the microporous particulate material.
90. The process of claim 89, wherein said heat treating comprises heating said slurry at a temperature sufficient to drive off sufficient water from said slurry, to form a free flowing bulk particulate.
91. The process of claim 90, wherein said heat treating further comprises calcining said free flowing bulk particulate.
92. The process of claim 89, wherein said heat treating comprises heating said slurry to dry, calcined powder in a.single step.
93. The process of claim 89, wherein said slurry comprises nitrate ions and during said heat treating is conducted at a temperature sufficient to decompose at least some of the nitrate ions to gaseous components.
94. The process of claim 91, wherein said slurry comprises nitrate ions and during said calcining is conducted at a temperature sufficient to decompose at least some of the nitrate ions to gaseous components.
95. The process of claim 89, wherein said process further comprises milling said rare earth metal oxide coated microporous particulate material to provide particle sizes in the range of 1 to 25 microns.
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